The corrosive influence of chloride ions preference adsorption on α-Al2O3 (0001) surface

Conductor-like screening model (COSMO), Periodic DFT calculations have been performed on a Al2O3 surface to model the influence of preference adsorption and interaction of chloride ions at increasing monolayer coverage on undefective passive film on Aluminum in solution environment. The results evidence that the critical monolayer of Cl- is 3/7, which is redefined. With increasing Cl- adsorption, both the first and second Cl- move from Al(1) atop and bridge10 sites to O(5) sites, suggesting that the weaker interaction between Cl- and Al2O3 surface but stronger interactions between three ions make the electrons uniformly occupy on the energy levels of them. More calculations shows that the preference adsorption sites of Cl- are independent of the surface area of oxide, and the adsorption energy decrease in three steps, each adsorption energy step only relate to the adsorption site and the morphology. On undefective oxide film, low coverage Cl- adsorption would restrain surface breakdown to happen which is consistent with the experiment results. (C) 2015 Elsevier B.V. All rights reserved.